technically this isn't a workout, but you could naturally start increasing your breast size by using massage techniques. They increase the blood-flow to the breasts, causing more of your body's estrogen to be carried there and to bind with the estrogen receptors.....also, it increases the production of prolactin, a naturally occurring hormone that increases breast size.
Here's a good link for breast massage technique
http://naturalremedysite.blogspot.com/2007/11/increase-cup-size-in-30-days-with.html and to maximize this, you could eat ground flaxseed (preferably a half cup per day), which contains ligands, which are not truly estrogens, but estrogen receptor agonists, or in simple terms, bind to and activate the estrogen receptors....this would potentially start feminizing you slowly, but without medication.
Feminizing occurs faster when taken with antiandrogens......a suppliment of pygeum bark is a good natural antiandrogen, and works great when combined with spearmint, peppermint, nettle, and saw palmetto, which also are all antiandrogens.
Taking natural antiandrogens and consuming flaxseed on top of massage would be a great way to start femininzing your body without synthetic drugs, and may make it less of a shock when you get onto hrt, as the process would already have begun